WO2013142956A1 - Procédés et composés pour la photogénération d'acides de lewis et leurs utilisations - Google Patents

Procédés et composés pour la photogénération d'acides de lewis et leurs utilisations Download PDF

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WO2013142956A1
WO2013142956A1 PCT/CA2013/000214 CA2013000214W WO2013142956A1 WO 2013142956 A1 WO2013142956 A1 WO 2013142956A1 CA 2013000214 W CA2013000214 W CA 2013000214W WO 2013142956 A1 WO2013142956 A1 WO 2013142956A1
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substituted
alkoxy
aryloxy
aryl
halogen
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PCT/CA2013/000214
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Warren Edward Piers
Andrey Yur'evich KHALIMON
Adam John VON MARWITZ
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Uti Limited Partnership
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/06—Preparatory processes
    • C08G77/08—Preparatory processes characterised by the catalysts used
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
    • C07F1/02—Lithium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/027—Organoboranes and organoborohydrides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
    • C07F7/0827—Syntheses with formation of a Si-C bond
    • C07F7/0829—Hydrosilylation reactions

Definitions

  • This invention relates to photo-activated Lewis acids generators, their synthesis and use.
  • Typical commercially available PAGs consist of triphenylsulfonium salts(4) that release protons upon irradiation with 254 nm wavelength light. Despite advances in the practice of this chemistry, the reactions that protons can amplify are limited and so the ability to photochemically liberate more versatile Lewis acid catalysts is desirable.
  • Lewis acids are the perfluoroarylboranes,(5) typified by the simplest member, f 7s-(pentafluorophenyl)borane, B(C6F 5 )3.
  • B(C 6 F 5 )3 exhibits strong Lewis acidity, high thermal stability, and air and water tolerance.
  • the inventors describe here a class of compounds containing a "masked” Lewis acid.
  • the Lewis acid can be released in situ under controlled conditions, as by e.g., exposure to ultraviolet light.
  • the compounds can generally be represented as a compound having the formula ([(AEX ( 3-n))(n+i)Yn] (n+1 )" )m(Q m+ )(n+i) (I), in which: AEX (3-n ) is a Lewis acid in which E is boron (B) or aluminum (Al); A is H- or R 1 R 2 NC(0)0- or R R 2 N- or R 3 0-, or R 4 OC(0)0-; and X is an aryl substituent e.g., a phenyl group; and Y is of the formula -(Ar 1 )EAX2 in which Ar 1 is arylene.
  • Y is absent from (AEX ⁇ 3-n))(n+i)Yn and is the maksed Lewis acid AEX 3 which bears a negative charge of minus 1 (1-).
  • Ar 1 may be viewed as a linker between two groups AEX2, each group containing a masked Lewis acid.
  • AEX2-Ar 1 -EX2A bears a negative charge of minus 2 (2-).
  • a photoacid generator (PAG) is used, the PAG photolytically reacting with A of AEX3 or AEX 2 -Ar 1 -EX2A to release Lewis acid AEX3 or " EX2". It is preferred that the PAG be counteraction Q of compound of formula (I).
  • Group X can be an aryl group having the formula -C 6 R a R b R c R d R e .
  • R a , R b , R c , R d , and R e are selected independently of each other and may be same or different, and may be any of the following: H, halogen, lower alkyl, or aryl group. It should be noted here, that when discussing radical portions of a molecule, such as "-C 6 R a R b R c R d R e ", "R a ", etc., the connecting bond may be omitted in various contexts for the sake of convenience, and the skilled person understands this.
  • Preferred X-groups of EX 3 are C6H5, -C6F H, p-CeH ⁇ , C 6 CI 5l and C 6 F 5 .
  • X- groups can be the same or different from each other.
  • R and R 2 of the R 1 R 2 NC(0)0- group or R 1 R 2 N- group can be separate pendant groups and can be selected independently of the other or they can form a ring together with the nitrogen to which they are attached.
  • R 1 R 2 are selected such that the pK a of the conjugate acid of R 1 R 2 NH is no more than about 12.
  • the pK a is between -5 and 12, or between -5 and 11 , or between -5 and 10, or between -5 and 9, or between -5 and 8, or between -5 and 7, or between -5 and 6, or between -5 and 5, or between -5 and 4, or between -5 and 3, or between -5 and 3, or between -5 and 2, or between -5 and 1 , or between -5 and 0.
  • the pK a of the conjugate acid, R R 2 NH 2 + can be about -6, about -5, about -4, about -3, about -2, about -1 , about 0, about 1 , about 2, about 3, about 4, about 5, about 6, about 7, about 8, about 9, about 10 or about 11.
  • R 1 , R 2 and N together form a heterocyclic radical containing 5 or 6 atoms and the cycle has 1 or 2 benzene rings fused with it. Any one or more of the hydrogen atoms of the rings is optionally, and independently, replaced by a substituent selected from the group:
  • alkyl including:
  • halogen-substituted alkyl nitro-substituted alkyl, aryl-substituted alkyl, alkoxy- substituted alkyl, aryloxy-substituted alkyl, alkylthio-substituted alkyl;
  • alkenyl including:
  • halogen-substituted alkenyl nitro-substituted alkenyl, aryl-substituted alkenyl, alkoxy-substituted alkenyl, aryloxy-substituted alkenyl, alkylthio-substituted alkenyl;
  • alkynyl including:
  • halogen-substituted alkynyl nitro-substituted alkynyl, aryl-substituted alkynyl, alkoxy-substituted alkynyl, aryloxy-substituted alkynyl, alkylthio-substituted alkynyl;
  • alkoxy including:
  • halogen-substituted alkoxy nitro-substituted alkoxy, aryl-substituted alkoxy, alkoxy-substituted alkoxy, aryloxy-substituted alkoxy, alkylthio-substituted alkoxy;
  • aryloxy including: halogen-substituted aryloxy, nitro-substituted aryloxy, aryl-substituted aryloxy, alkoxy-substituted aryloxy, aryloxy-substituted aryloxy, alkylthio-substituted aryloxy;
  • alkylthio including:
  • halogen-substituted alkylthiol nitro-substituted alkylthiol, aryl-substituted alkylthiol, alkoxy-substituted alkylthiol, aryloxy-substituted alkylthiol, alkylthio- substituted alkylthiol;
  • alkylsulfonyl including:
  • halogen-substituted alkylsulfonyl nitro-substituted alkylsulfonyl, aryl- substituted alkylsulfonyl, alkoxy-substituted alkylsulfonyl, aryloxy-substituted alkylsulfonyl, alkylthio-substituted alkylsulfonyl.
  • Any one or more of the hydrogen atoms of the ring is optionally, and independently, replaced by a substituent selected from the group:
  • alkyl including:
  • halogen-substituted alkyl nitro-substituted alkyl, aryl-substituted alkyl, alkoxy- substituted alkyl, aryloxy-substituted alkyl, alkylthio-substituted alkyl;
  • alkenyl including:
  • halogen-substituted alkenyl nitro-substituted alkenyl, aryl-substituted alkenyl, alkoxy-substituted alkenyl, aryloxy-substituted alkenyl, alkylthio-substituted alkenyl;
  • alkynyl including:
  • halogen-substituted alkynyl nitro-substituted alkynyl, aryl-substituted alkynyl, alkoxy-substituted alkynyl, aryloxy-substituted alkynyl, alkylthio-substituted alkynyl;
  • alkoxy including:
  • halogen-substituted alkoxy nitro-substituted alkoxy, aryl-substituted alkoxy, alkoxy-substituted alkoxy, aryloxy-substituted alkoxy, alkylthio-substituted alkoxy; aryloxy, including:
  • halogen-substituted aryloxy nitro-substituted aryloxy, aryl-substituted aryloxy, alkoxy-substituted aryloxy, aryloxy-substituted aryloxy, alkylthio-substituted aryloxy;
  • alkylthio including:
  • halogen-substituted alkylthiol nitro-substituted alkylthiol, aryl-substituted alkylthiol, alkoxy-substituted alkylthiol, aryloxy-substituted alkylthiol, alkylthio- substituted alkylthiol;
  • alkylsulfonyl including:
  • halogen-substituted alkylsulfonyl nitro-substituted alkylsulfonyl, aryl- substituted alkylsulfonyl, alkoxy-substituted alkylsulfonyl, aryloxy-substituted alkylsulfonyl, alkylthio-substituted alkylsulfonyl.
  • R 1 , R 2 are pendant radicals that are, independently of each other, linear, branched or cyclic alkyi, heterocyclic alkyi, or aryl, wherein any one or more of the hydrogen atoms of an alkyi or aryl group is optionally, and independently, replaced by a substituent selected from the group:
  • alkyi including:
  • halogen-substituted alkyi nitro-substituted alkyi, aryl-substituted alkyi, alkoxy- substituted alkyi, aryloxy-substituted alkyi, alkylthio-substituted alkyi;
  • alkenyl including:
  • halogen-substituted alkenyl nitro-substituted alkenyl, aryl-substituted alkenyl, alkoxy-substituted alkenyl, aryloxy-substituted alkenyl, alkylthio-substituted alkenyl;
  • alkynyl including:
  • halogen-substituted alkynyl nitro-substituted alkynyl, aryl-substituted alkynyl, alkoxy-substituted alkynyl, aryloxy-substituted alkynyl, alkylthio-substituted alkynyl;
  • alkoxy including: halogen-substituted alkoxy, nitro-substituted alkoxy, aryl-substituted alkoxy, alkoxy-substituted alkoxy, aryloxy-substituted alkoxy, alkylthio-substituted alkoxy;
  • aryloxy including:
  • halogen-substituted aryloxy nitro-substituted aryloxy, aryl-substituted aryloxy, alkoxy-substituted aryloxy, aryloxy-substituted aryloxy, alkylthio-substituted aryloxy;
  • alkylthio including:
  • halogen-substituted alkylthiol nitro-substituted alkylthiol, aryl-substituted alkylthiol, alkoxy-substituted alkylthiol, aryloxy-substituted alkylthiol, alkylthio- substituted alkylthiol;
  • alkylsulfonyl including:
  • halogen-substituted alkylsulfonyl nitro-substituted alkylsulfonyl, aryl- substituted alkylsulfonyl, alkoxy-substituted alkylsulfonyl, aryloxy-substituted alkylsulfonyl, alkylthio-substituted alkylsulfonyl.
  • R 3 can be linear, branched or cyclic alkyl, heterocyclic alkyl, or aryl, wherein any one or more of the hydrogen atoms of an alkyl or aryl group is optionally, and independently, replaced by a substituent selected from the group:
  • alkyl including:
  • halogen-substituted alkyl nitro-substituted alkyl, aryl-substituted alkyl, alkoxy- substituted alkyl, aryloxy-substituted alkyl, alkylthio-substituted alkyl;
  • alkenyl including:
  • halogen-substituted alkenyl nitro-substituted alkenyl, aryl-substituted alkenyl, alkoxy-substituted alkenyl, aryloxy-substituted alkenyl, alkylthio-substituted alkenyl;
  • alkynyl including:
  • halogen-substituted alkynyl nitro-substituted alkynyl, aryl-substituted alkynyl, alkoxy-substituted alkynyl, aryloxy-substituted alkynyl, alkylthio-substituted alkynyl;
  • alkoxy including: halogen-substituted alkoxy, nitro-substituted alkoxy, aryl-substituted alkoxy, alkoxy-substituted alkoxy, aryloxy-substituted alkoxy, alkylthio-substituted alkoxy;
  • aryloxy including:
  • halogen-substituted aryloxy nitro-substituted aryloxy, aryl-substituted aryloxy, alkoxy-substituted aryloxy, aryloxy-substituted aryloxy, alkylthio-substituted aryloxy;
  • alkylthio including:
  • halogen-substituted alkylthiol nitro-substituted alkylthiol, aryl-substituted alkylthiol, alkoxy-substituted alkylthiol, aryloxy-substituted alkylthiol, alkylthio- substituted alkylthiol;
  • alkylsulfonyl including:
  • halogen-substituted alkylsulfonyl nitro-substituted alkylsulfonyl, aryl- substituted alkylsulfonyl, alkoxy-substituted alkylsulfonyl, aryloxy-substituted alkylsulfonyl, alkylthio-substituted alkylsulfonyl.
  • R 4 can be linear, branched or cyclic alkyl, heterocyclic alkyl, or aryl, wherein any one or more of the hydrogen atoms of an alkyl or aryl group is optionally, and independently, replaced by a substituent selected from the group:
  • alkyl including:
  • halogen-substituted alkyl nitro-substituted alkyl, aryl-substituted alkyl, alkoxy- substituted alkyl, aryloxy-substituted alkyl, alkylthio-substituted alkyl;
  • alkenyl including:
  • halogen-substituted alkenyl nitro-substituted alkenyl, aryl-substituted alkenyl, alkoxy-substituted alkenyl, aryloxy-substituted alkenyl, alkylthio-substituted alkenyl;
  • alkynyl including:
  • halogen-substituted alkynyl nitro-substituted alkynyl, aryl-substituted alkynyl, alkoxy-substituted alkynyl, aryloxy-substituted alkynyl, alkylthio-substituted alkynyl;
  • alkoxy including: halogen-substituted alkoxy, nitro-substituted alkoxy, aryl-substituted alkoxy, alkoxy-substituted alkoxy, aryloxy-substituted alkoxy, alkylthio-substituted alkoxy;
  • aryloxy including:
  • halogen-substituted aryloxy nitro-substituted aryloxy, aryl-substituted aryloxy, alkoxy-substituted aryloxy, aryloxy-substituted aryloxy, alkylthio-substituted aryloxy;
  • alkylthio including:
  • halogen-substituted alkylthiol nitro-substituted alkylthiol, aryl-substituted alkylthiol, alkoxy-substituted alkylthiol, aryloxy-substituted alkylthiol, alkylthio- substituted alkylthiol;
  • alkylsulfonyl including:
  • halogen-substituted alkylsulfonyl nitro-substituted alkylsulfonyl, aryl- substituted alkylsulfonyl, alkoxy-substituted alkylsulfonyl, aryloxy-substituted alkylsulfonyl, alkylthio-substituted alkylsulfonyl.
  • Ar 1 is effectively a linker between two masked Lewis groups of the moiety AEX 2 -Ar 1 -EX 2 A.
  • Ar 1 is preferably a bivalent phenyl, which can bear substituents.
  • Ar 1 has formula C 6 R a1 R b1 R c R d1 , and R a1 , R b , R c1 , and R d1 substituents for hydrogen can be, for example, any of halogen, lower alkyl and aryl group, and so Ar1 can be the same or different from each other e.g., C 6 F 4 , C 6 F 3 H, C 6 F 2 H 2 , C 6 FH 3 , C 6 CI 4 , C 6 CI 3 H, C 6 CI 2 H 2 , C 6 CIH 3 , C 6 H 4 , etc.
  • the bivalent group is CeF 4) and the phenyl ring attaches to B atoms at p
  • Combination of [AEX 3 ] ⁇ [Q] + and reactants, for example those of a Piers-Rubinsztajn reaction, can thus lead to photo-controlled in situ generation of the Lewis acid thereby lending control to the chemical reaction catalyzed by the Lewis acid.
  • Q of the salt [AEX 3 ] " m [Q] m+ is a mixture of PAGs, or a mixture of a PAG and other cationic counterion, or can be other than a PAG.
  • a PAG of the invention is generally a cationic species that ejects protons upon irradiation at a defined wavelength.
  • a PAG is a counterion of the masked Lewis acid of the invention.
  • Preferred families of PAGs are iodinium and sulfonium compounds: R A R B I + and R A R B R C S + .
  • R A and R B are aryl, and preferably both of R A and R B are aryl.
  • the other of R A and R B may be optionally substituted alkyl.
  • the aryl group may be substituted at any of its positions, and preferably o-, m- and/or p-substituted, preferably p-substituted, with respect to the halogen atom of the cation. Any substitution at a given position is made independently of substitutions at other positions.
  • Substituents are preferably selected from the group:
  • alkyl including:
  • halogen-substituted alkyl nitro-substituted alkyl, aryl-substituted alkyl, alkoxy- substituted alkyl, alkylthio-substituted alkyl;
  • alkoxy including:
  • halogen-substituted alkoxy nitro-substituted alkoxy, aryl-substituted alkoxy, alkoxy-substituted alkoxy, alkylthio-substituted alkoxy;
  • aryloxy including:
  • halogen-substituted aryloxy nitro-substituted aryloxy, aryl-substituted aryloxy, alkoxy-substituted aryloxy, alkylthio-substituted aryloxy;
  • alkylthio including:
  • halogen-substituted alkylthiol nitro-substituted alkylthiol, aryl-substituted alkylthiol, alkoxy-substituted alkylthiol, alkylthio-substituted alkylthiol;
  • alkylsulfonyl including:
  • halogen-substituted alkylsulfonyl nitro-substituted alkylsulfonyl, aryl- substituted alkylsulfonyl, alkoxy-substituted alkylsulfonyl, alkylthio-substituted alkylsulfonyl.
  • a preferred aryl group is phenyl, which if substituted, is preferably p-substituted with halogen, alkoxy, aryloxy or alkyl.
  • a preferred alkyl group is f-butyl.
  • Preferred iodiniums include those in which R A and R B are the same as each other.
  • R A , R B and R c are aryl, and preferably at least two of R A , R B and R c are aryl.
  • Each aryl group may be substituted at any of its positions, and preferably o-, m- and/or p-substituted, preferably p-substituted, with respect to the sulfur atom of the cation. Any substitution at a given position is made independently of substitutions at other positions.
  • Substituents are preferably selected from the group:
  • alkyl including:
  • halogen-substituted alkyl nitro-substituted alkyl, aryl-substituted alkyl, alkoxy- substituted alkyl, alkylthio-substituted alkyl;
  • alkoxy including:
  • halogen-substituted alkoxy nitro-substituted alkoxy, aryl-substituted alkoxy, alkoxy-substituted alkoxy, alkylthio-substituted alkoxy;
  • aryloxy including:
  • halogen-substituted aryloxy nitro-substituted aryloxy, aryl-substituted aryloxy, alkoxy-substituted aryloxy, alkylthio-substituted aryloxy;
  • alkylthio including:
  • halogen-substituted alkylthiol nitro-substituted alkylthiol, aryl-substituted alkylthiol, alkoxy-substituted alkylthiol, alkylthio-substituted alkylthiol;
  • alkylsulfonyl including:
  • halogen-substituted alkylsulfonyl nitro-substituted alkylsulfonyl, aryl- substituted alkylsulfonyl, alkoxy-substituted alkylsulfonyl, alkylthio-substituted alkylsulfonyl.
  • Preferred aryl groups are phenyl and naphthyl. Preferred are p-substituents selected from halogen, alkoxy, arloxy or alkyl. Preferably, if one of R A , R B and R c is not aryl, the third group is alkyl, preferably lower alkyl. It is also preferred that, if all of R A , R B and R c are aryl, that two of R A , R B and R c be same as each other.
  • examples of PAGs, [Q] + include:
  • Figure 1 shows the solid-state structure of PhLAG 10
  • Figure 2 shows the solid-state structure of PhLAG 5 (second ferf-butyl group is omitted for clarity);
  • Figure 3 shows the solid-state structure of PhLAG 12
  • Figure 4 shows a TGA/DSC diagram for PhLAG 5
  • Figure 5 shows a TGA/DSC diagram for PhLAG 6
  • Figure 6 shows a TGA/DSC diagram for PhLAG 10
  • Figure 7 shows a TGA/DSC diagram for PhLAG 11
  • Figure 8 shows a TGA diagram for PhLAG 12
  • Figure 9 shows a TGA diagram for PhLAG 21
  • Figure 10 shows a TGA diagram for PhLAG 18
  • Figure 11 shows the UV-vis spectrum of bis(te/ ⁇ -butyl)carbazole in CH 2 CI 2 (1.1 -10- 5 mol/L);
  • Figure 12 shows the UV-vis spectrum of borate 4 in CH 2 CI 2 (1.1 -10 "5 mol/L);
  • Figure 13 shows the UV-vis spectrum of 5 in CH 2 CI 2 (1.1 -10 "5 mol/L);
  • Figure 14 shows the UV-vis spectrum of 6 in CH 2 CI 2 (1.0-10 "5 mol/L);
  • Figure 15 shows the UV-vis spectrum of 10 in CH 2 CI 2 (1.1 -10 "5 mol/L);
  • Figure 16 shows the UV-vis spectrum of 11 in CH 2 CI 2 (1.1 - 10 "5 mol/L);
  • Figure 17 shows the UV-vis spectrum of 12 in CH 2 CI 2 (1.1 -10 5 mol/L);
  • Figure 18 shows the UV-vis spectrum of 21 in CH 2 CI 2 (1.1 -10 "5 mol/L);
  • Figure 19 shows the UV-vis spectrum of 18 in CH 2 CI 2 (1.1 -10 "5 mol/L);
  • Figure 20 shows the UV-vis spectrum of 19 in CH 2 CI 2 (1.1 -10 "5 mol/L);
  • Figure 21(A) shows the kinetic profile for decomposition of 5 in CD3CN (2.1 -10 "3 mol/L) to CD 3 CN B(C 6 F5)3 under 254 nm light
  • Figure 21(B) shows the kinetic profile for formation of CD 3 CN-B(C 6 F5)3 from a solution of 5 in CD ⁇ I ⁇ CDsCN (8.7/1 ) (2.5- 10 "3 mol/L) under 254 nm light;
  • Figure 22 shows kinetic profiles for decomposition of 6 (A) and 10 (B) in CD3CN (2.1 - 10 3 mol/L) to CD 3 CN-B(C 6 F 5 )3 under 254 nm light;
  • Figure 23 shows kinetic profile for decomposition of 11 in CD 2 Cl2/CD 3 CN (8.7/1 )
  • Figure 24 shows a diagram comparing the thickness of tefra-TMCTS films with PhLAG 5 (1 wt %) as deposited and after thermal treatment (105 °C, 1 min) and/or photolysis (254 nm, 150 mJ/cm 2 ) and rinse with 2-heptanone;
  • Figure 25 shows a series of IR spectra for fe/ra-TMCTS thin films with PhLAG 5 (1 wt %) as deposited after thermal treatment (105 °C, 1 min) and/or photolysis (254 nm, 150 mJ/cm 2 );
  • Figure 26 shows fractional change in peak area in IR spectra of fefra-TMCTS thin films with PhLAG 5 (1 wt %) as deposited, after exposure to 254 nm light (150 mJ/cm 2 ) and/or thermal treatment (105 °C, 1 min); and
  • Halo or halogen refers to fluorine, chlorine, bromine or iodine.
  • AlkyI is a branched, linear or cyclic hydrocarbon structure having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms and more preferably 1 to 8 carbon atoms.
  • “Lower alkyl” is a subset of this group having 1 to 6, more preferably 1 to 4 carbon atoms.
  • the alkyl group is cyclic, it may also be referred to as a cycloalkyl group.
  • an alkyl residue having a specific number of carbons is named, all geometric isomers having that number of carbons are intended to be encompassed; thus, for example, "butyl” is meant to include n-butyl, sec-butyl, iso-butyl and t-butyl, etc.
  • Alkyl can also be used herein to denote an alkyl residue as part of a larger functional group and when so used, is taken together with other atoms to form another functional group.
  • -C(0)Oalkyl is an ester group. This applies to other groups capable being combined with other groups such as alkenyl, etc.
  • Alkenyl is a hydrocarbon structure of 2 or more carbon atoms, such as 2 to 10 carbon atoms and more preferably 2 to 6 carbon atoms and having at least 1 site of alkenyl unsaturation.
  • Alkynyl is a hydrocarbon structure preferably having from 2 to 10 carbon atoms and more preferably 3 to 6 carbon atoms and having at least 1 site of alkynyl unsaturation i.e., a triple bond such as the moiety -C ⁇ CH, or -C ⁇ C-CH 2 CH 2 C ⁇ CH, -CH 2 -C ⁇ C-CH2CH2CH 2 CH3, etc.
  • a radical e.g., an alkyl or alkenyl radical
  • a halogen-substituted alkyl group this means that one or more of the hydrogen atoms of the named radical is replaced by the substituent indicated, as in this example a halogen.
  • a halogen-substituted alkyl group examples are thus -CH2CH2F, -CH2CCI3, -CH2CH2CF2CF2CF3, etc.
  • Aryl is a monocyclic, bicyclic or tricyclic aromatic group in which cyclic structure(s) are composed of carbon atoms. Examples include the phenyl, naphthyl groups. Preferred aromatics are those in which the aromatic rings are fused to each other such as in naphthyl.
  • the atom represented by "E” e.g., B is covalently bonded directly a carbon atom of an aromatic cycle.
  • Cycloalkyl is a cyclic alkyl group having 3 or more carbon atoms. Examples of cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl.
  • Heterocycloalkyl refers to a cycloalkyl residue in which one to four of the carbons forming the ring is replaced by a heteroatom such as nitrogen or sulfur.
  • heterocycloalkyls whose radicals are heterocyclic groups include pyrrolidine, piperidine and thiazolidine.
  • Heteroaryl is a heterocyclic aromatic ring containing 1 to 6 heteroatoms selected from oxygen, sulfur and nitrogen, preferably nitrogen or sulfur, and 1-20 carbon atoms.
  • heteroaryls whose radicals are heterocyclic groups include carbazole and pyrrole.
  • Heterocyclic refers to a heterocycloalkyl or heteroaryl residue.
  • Alkoxy refers to an alkyl group that is connected to the parent structure through an oxygen atom i.e., -O-alkyl.
  • a cycloalkyl group When a cycloalkyl group is connected to the parent structure through an oxygen atom, the group may also be referred to as a cycloalkoxy group. Examples include methoxy, ethoxy, propoxy, isopropoxy, cyclopropyloxy, cyclohexyloxy and the like.
  • Aryloxy refers to an aryl group that is connected to the parent structure through an oxygen atom i.e., -O-aryl.
  • Perhalo used in connection with group containing hydrogen atoms e.g., a perhaloalkyl group means that all hydrogen atoms of the group are replaced by halogen.
  • An example of a perfluoroalkyl group is -CF 2 CF 2 CF 3 .
  • Alkylthio refers to an alkyl group that is connected to the parent structure through a sulfur atom i.e., -S-alkyl.
  • alkylthio radical examples include methylthio; ethylthio and isopropylthio.
  • Alkylsulfonyl refers to groups -SOaalkyl.
  • Arylene is a bivalent aryl group which in the context of a compound of ([AEX(2 ) Y] 2" )m(Q m+ )(2), the group covalently links the ⁇ " atoms i.e., Al or B of the compound.
  • R"-M is an organometallic compound such as n-butyl lithium and U is an anion e.g. CI " .
  • This aspect of the invention is exemplified by Examples 11-1 and II- 3.
  • R 1 R 2 are selected such that the pK a of the conjugate acid of R 1 R 2 NH is no more than about 12.
  • R 1 R 2 NH is carbazole the conjugate acid of which, R 1 R 2 NH 2 + , has a pK a of -4.94.( 75)
  • a pKa determination can be made as described by A. Albert and E. P. Serjeant, in Ionization Constants of Acids and Bases, (New York, Wiley, 1962).
  • the PAG component of a compound of the invention may be any compound capable of generating an acid, H + , upon exposure to actinic radiation such as ultraviolet or other radiation suitable to the circumstances.
  • the PAG can be selected so as to be activated at wavelength(s) suitable to the context in which the Lewis acid is generated.
  • a PAG may thus be selected such that the Lewis acid is generated by PAG activation at a predetermined wavelength.
  • An activation wavelength can be between 220 nm and 260 nm, 310 to 365 nm, or more generally somewhere between 150 and 450 nm.
  • Exemplary sulfonium and iodinium cationic PAGs in addition to those described above, are also described in columns 81 and 82 of United States Patent No. 8,114,571 ,(76).
  • Preferred compounds of the invention are as follows:
  • R 1 H, Alkyl
  • Aryl R 2 H, Alkyl
  • Aryl R 3 H, Alkyl
  • Aryl E B, Al
  • Types A-E R 1 R 2 NC(0)0-, R R 2 N- H-, R 3 0- , p-C 6 F 4 H, p-C 6 H 4 F R 4 OC(0)0- s, C6H5
  • transition metal(s) in the compound preferably less than 1%, or less than 0.1%, or less than 0.01 %, or less than 0.001% by weight of transition metal(s) in the compound. Most preferably, there is no traceable amount of transition metal(s) in the compound.
  • Tris(pentafluorophenyl) borane, B(C 6 F 5 ) 3 was sublimed at 65 °C under high dynamic vacuum, dried over Me 2 Si(H)CI for 4 h and re-sublimed under the same conditions after vacuum removal of volatiles.
  • Ph 3 SCI was purchased from Sigma-Aldrich and used without further purification.
  • 3,6-di-(ferf-butyl)carbazole was prepared according to the literature procedure.(77) [K][HB(C 6 F 5 ) 3 ] was synthesized using previously published procedure ⁇ 18)
  • Carbon dioxide gas ( ⁇ 2 atm) was added via vacuum transfer to a suspension of 1 (2.02 g, 7.06 mmol) in 100 mL of toluene. The mixture was sonicated for 30 min and then stirred at room temperature for 30 min. All volatiles were pumped off to leave an oily residue which was washed with hexanes (100 mL) and dried in vacuum. The resulting white solid was suspended in 100 mL of dichloromethane and ⁇ , ⁇ , ⁇ ', ⁇ '- tetramethylethylenediamine (TMEDA) (1.06 mL, 7.07 mmol) was added in one portion at room temperature. The mixture was allowed to stir at room temperature for 10 min.
  • TEDA ⁇ , ⁇ , ⁇ ', ⁇ '- tetramethylethylenediamine
  • Figure 1 were grown by slow vaporization of hexanes into a toluene solution at -30
  • a round bottom flask containing phenol (0.0184g, 0.195 mmol), B(C 6 F 5 ) 3 (0.100 g, 0.195 mmol) and potassium hydride (0.008g, 0.200 mmol) was equipped with a sealable Kontes valve and 5 ml_ of dichloromethane was condensed into the reaction flask at -78 °C. Immediate hydrogen evolution was observed and the solution was allowed to warm to room temperature and stir for 1 hour. At this point the cloudy white solution was filtered through an Acrodisc followed by removal of all volatiles. The remaining white residue was washed/sonicated with hexane and after decanting off the solvent the product was dried under vacuum to give a white powder.
  • Triphenylsulfonium chloride (0.016 g, 0.054 mmol) was added to a stirring dichloromethane (4 ml_) solution of [K][PhO-B(C 6 F 5 ) 3 ] (0.035 g, 0.054 mmol). The reaction is left to stir for 1 hour at room temperature at which point the KCI byproduct was filtered off using an Acrodisc and all volatiles are removed in vacuum. The resulting white powder was washed with hexane and dried at reduced pressure to give a fluffy white powder. Yield 36 mg (77%).
  • UV-visible spectra of 3,6-di-(terf-butyl)carbazole, borate 4 and PhLAGs 5, 6, 10, 11 , 12, 18, 19, and 21 are shown in Figures 11-20, respectively.
  • the values of of Anax (nm) and ⁇ (10 3 M “1 cm “1 ) for [Ph 3 S][OTf], 3,6-di-(fe/t-butyl)carbazole, lithium borate 4, and PhLAGs 5, 6, 10, 11 , 12, 18, 19, and 21 are summarized in Table 1.
  • Method A A solution of either 5, 6, 10, 12 or 18 in acetonitrile-d 3 (2.1 - 10 "3 mol/L) was placed into a quartz NMR tube. No reaction was observed in the absence of UV light during 12 hours at room temperature. The samples were exposed to 254 nm light for 12-20 min showing by NMR spectroscopy formation of an adduct of B(C6F 5 ) 3 with acetonitrile-d 3 (67% conversion of 5 in 20 min (58% conversion in 12 min), 81% conversion of 6 in 12 min, 46% conversion of 10 in 13 min, 99% conversion of 12 in 12 min, and 60% conversion of 18 in 12 min; see Table 2(A) and Figures 21(A) and 22).
  • Method B CD 3 CN (65.3 ⁇ _, 1.25-10 "3 mmol) was added to a solution of either 5, 6, 11 , 12, or 21 (1.25-10 "3 mmol) in 0.5 mL of CD 2 CI 2 in a quartz NMR tube. No reaction was observed in the absence of UV light within 12 h at room temperature.
  • the sample was exposed to 254 nm light and followed by NMR spectroscopy for 5- 12 min showing formation of an adduct of B(CeF 5 ) 3 with acetonitrile-d 3 or an adduct of 1 ,4- ⁇ (C 6 F5)2B ⁇ 2 C 6 F 4 with acetonitrile-d 3 (for PhLAG 21 ) (99% conversion of 5 in 12 min, 81 % conversion of 6 in 5 min, 99% conversion of 11 in 12 min, 99% conversion of 12 in 5 min, and 90% conversion of 21 in 5 min; see Table 2(B) and Figures 21(A) and 23).
  • PhLAgs 16, 18, and 19 pKa values of the alcohol forming upon exposure to 254 nm light should be higher than 8 (Ballinger, P.; Long, F. A. Journal of the American Chemical Society 1959, 81, 1050; Ballinger, P.; Long, F. A. Journal of the American Chemical Society 1960, 82, 795. Haszeldine, R. N. Journal of the Chemical Society 1953, 1757) to prevent any side reactions, such as protonation of B(C 6 F 5 ) 3 to form ROB(C 6 F 5 ) 2 and C 6 F 5 H.
  • Hydrosilane was added in one portion at room temperature to a solution of substrate (0.25 mol/L) and 5 (1 mol % to the substrate) in either CD 2 CI 2 or CH 2 CI 2 .
  • the resulting mixture was placed in either quartz NMR or quartz test tube under argon atmosphere. No reaction was observed in the absence of UV light within 1 hour at room temperature.
  • the samples were exposed to 254 nm light for 15 min. Conversion of organic substrates was determined by H NMR spectroscopy using Si(SiMe 3 ) as a standard (Table 3).
  • PhC(0)0'Bu (5 wt % to solvent), PhLAG 5 (5 mmol/L), and Si(SiMe 3 )4 (internal standard; 1 mol % to PhCiOJO'Bu) were mixed together in CD 2 CI 2 in a quartz NMR tube under argon atmosphere. The mixture was left at room temperature and ambient light for one hour showing no reaction by NMR spectroscopy. After that the sample was exposed to 254 nm light for 30 min. NMR analysis revealed 29% conversion of PhC(0)0'Bu to PhC(0)OH and isobutene (Table 5, entry 3). Control experiments without PhLAG 5 (Table 5, entry 1 ) or in the presence of large excess (ca.
  • TMCTS 2,4,6,8-tetramethylcyclotetra- siloxane TMCTS was dissolved in 40 mL of anhydrous toluene in a 250 mL PTFE bottle. To this solution was added 10 mg (0.02 mmol) of B(C 6 F 5 ) 3 followed by slow addition of 0.65 g (3.125 mmol) of tetraethyl orthosilicate (TEOS) dissolved in 10 mL toluene. Immediate bubbling is observed and the reaction mixture heats up moderately.
  • TEOS tetraethyl orthosilicate
  • PhMeC(O) 10 >99 PhMeCH(OSiEt 3 ) 2 PhHC(O) 5 >99 PhCH 2 (OSiEt 3 )
  • an individual compound or element as a member of a class component of a composition of the invention is a disclosure the individual compound or element as part of a composition of the invention.

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Abstract

L'invention porte sur des acides de Lewis masqués sous la forme de composés, l'acide de Lewis pouvant être libéré par exposition du composé à de la lumière, en particulier de la lumière ultraviolette. Ces composés peuvent être représentés par la formule (I) suivante : ([(AEX(3-n))(n+1)Yn](n+1)-)m(Qm+)(n+1) (I). Dans la formule, en bref, E représente le bore ou l'aluminium, X représente un groupe aryle et Y représente -Ar'EAX. Ces composés sont utilisés comme catalyseur pour une réaction d'hydrosilylation, la réticulation de polymères ou des réactions de déprotection d'ester en tant que photogénérateur d'acide de Lewis (PhLAG).
PCT/CA2013/000214 2012-03-28 2013-03-08 Procédés et composés pour la photogénération d'acides de lewis et leurs utilisations WO2013142956A1 (fr)

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JP2017014137A (ja) * 2015-06-30 2017-01-19 カーリットホールディングス株式会社 光酸発生剤及び感光性組成物
WO2019068357A1 (fr) * 2017-10-06 2019-04-11 Wacker Chemie Ag Préparation de siloxanes en présence de composés silicium(ii) cationiques
JPWO2018105537A1 (ja) * 2016-12-08 2019-10-31 株式会社日本触媒 光ルイス酸発生剤
WO2020025144A1 (fr) * 2018-08-03 2020-02-06 Wacker Chemie Ag Procédé de préparation d'organosiloxanes possédant des groupes triorganosilyloxy
WO2020131365A1 (fr) * 2018-12-21 2020-06-25 Dow Silicones Corporation Procédé de préparation d'un polyorganosiloxane fonctionnalisé
US11643506B2 (en) 2018-12-21 2023-05-09 Dow Silicones Corporation Polyfunctional organosiloxanes, compositions containing same, and methods for the preparation thereof
US11685817B2 (en) 2019-06-04 2023-06-27 Dow Silicones Corporation Bridged frustrated Lewis pairs as thermal trigger for reactions between Si-H and epoxide
US11787908B2 (en) 2018-12-21 2023-10-17 Dow Silicones Corporation Methods for making polyfunctional organosiloxanes and compositions containing same
US11905375B2 (en) 2018-12-21 2024-02-20 Dow Silicones Corporation Polyfunctional organosiloxanes, compositions containing same, and methods for the preparation thereof

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JP2017014137A (ja) * 2015-06-30 2017-01-19 カーリットホールディングス株式会社 光酸発生剤及び感光性組成物
JPWO2018105537A1 (ja) * 2016-12-08 2019-10-31 株式会社日本触媒 光ルイス酸発生剤
WO2019068357A1 (fr) * 2017-10-06 2019-04-11 Wacker Chemie Ag Préparation de siloxanes en présence de composés silicium(ii) cationiques
CN110494440A (zh) * 2017-10-06 2019-11-22 瓦克化学股份公司 在阳离子硅(ii)化合物存在下制备硅氧烷
US11325923B2 (en) 2017-10-06 2022-05-10 Wacker Chemie Ag Preparation of siloxanes in the presence of cationic silicon (II) compounds
WO2020025144A1 (fr) * 2018-08-03 2020-02-06 Wacker Chemie Ag Procédé de préparation d'organosiloxanes possédant des groupes triorganosilyloxy
CN113166418A (zh) * 2018-12-21 2021-07-23 美国陶氏有机硅公司 用于制备官能化聚有机硅氧烷的方法
US20220041812A1 (en) * 2018-12-21 2022-02-10 Dow Silicones Corporation Method for preparing a functionalized polyorganosiloxane
WO2020131365A1 (fr) * 2018-12-21 2020-06-25 Dow Silicones Corporation Procédé de préparation d'un polyorganosiloxane fonctionnalisé
US11643506B2 (en) 2018-12-21 2023-05-09 Dow Silicones Corporation Polyfunctional organosiloxanes, compositions containing same, and methods for the preparation thereof
US11787908B2 (en) 2018-12-21 2023-10-17 Dow Silicones Corporation Methods for making polyfunctional organosiloxanes and compositions containing same
US11905375B2 (en) 2018-12-21 2024-02-20 Dow Silicones Corporation Polyfunctional organosiloxanes, compositions containing same, and methods for the preparation thereof
US11685817B2 (en) 2019-06-04 2023-06-27 Dow Silicones Corporation Bridged frustrated Lewis pairs as thermal trigger for reactions between Si-H and epoxide

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